Proceedings of the

Volume One 17th INTERNATIONAL CONGRESS OF

Sydney, NSW, Australia

July 22–28, 2017

Proceedings VOLUME 1

Edited by Kevin Moore Susan White 2017

Proceedings of the 17th International Congress of Speleology i 17th INTERNATIONAL CONGRESS OF SPELEOLOGY Sydney, NSW, Australia July 22–28, 2013 Proceedings VOLUME 1

Produced by the Organizing Committee of the 167th International Congress of Speleology. Published by the Australian Speleological Federation Inc and Speleo2017 in the co-operation with the International Union of Speleology.

Design by Kevin Moore Layout by Kevin Moore Printed in Victoria Australia Te contributions were assisted with language and edited. Contributions express author(s) opinion.

Recommended form of citation for this volume: Moore K., White S. (Eds), 2017. Proceedings of the 17th International Congress of Speleology, July 22–28, Sydney, NSW Australia Volume 1, Australian Speleological Federation Inc. Sydney.

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Cover photo : Keir Vaughan-Taylor on Lake 2, Koonalda , Nullarbor Plain. (Photo by Kevin Moore)

Back Cover : Te Khan and Beagum in Kubla Khan Cave Tasmania (Photo by Garry K. Smith) ii Proceedings of the 17th International Congress of Speleology Secondary Minerals From Italian Sulfuric Acid Ilenia Maria D’Angeli1, Jo De Waele1, Cristina Carbone2, Mario Parise3, Giuliana Madonia4, Marco Vattano4 Afliation: 1Department of Biological, Geological and Environmental Sciences, University of Bologna, Italy, [email protected]; [email protected] 2DISTAV, Dipartimento di Scienze della Terra, dell’Ambiente e della Vita, Università di Genova, Italy. E-mail: [email protected] 3Department of Earth and Environmental Sciences, University “Aldo Moro” of Bari, Italy (ex CNR-IRPI Bari, Italy) E-mail: [email protected] 4Dipartimento di Scienze della Terra e del Mare, University of Palermo, Italy. E-mail: [email protected]; [email protected]

Abstract Italy is a country hosting a large number of hypogenic sulfuric acid (SAS) speleogenesis caves, mostly located along the Apennine chain, but also in Campania (along the coastline of Capo Palinuro), Apulia (along the coastline of Santa Cesarea Terme) and Sicily.

Besides the typical morphologies related to their special geochemical origin (cupolas, replacement pockets, bubble trails, etc), these caves ofen host abundant secondary mineral deposits, mainly gypsum, being the result of the interaction between the sulfuric acid and the carbonate host rock. Native sulfur deposits are also visible on the ceiling and roof, and peculiar sulfuric acid minerals such as jarosite, alunite, and other sulfates like copiapite, pickeringite, tschermigite, tamarugite (probably related to the weathering of native clay minerals) have been found in those caves.

Te presence of typical SAS minerals, together with the morphologies, testifes the infuence of rising acidic waters, that likely interact with the deep-seated evaporite deposits (along the Apennine chain), with volcanic sources or hydrothermal springs in the Tyrrhenian sea (in Campania) and with marine waters that infltrate on the sea bottom and rise through deep faults (in Apulia). Tis paper describes the secondary minerals discovered in several caves, and discusses their origin and possible use in reconstructing the evolution of these cave systems.

Keywords: sulfates; speleogenesis; hypogenic caves; cave mineralogy

1. Introduction and Pieri 1964; Ciarapica et al. 1987) cropping out in several regions of Italy including Emilia-Romagna, Tuscany, Latium, Hypogene caves are widespread around the world and Umbria, Marche, Apulia (Gargano), and also in Greece and together with epigenic caves represent the most important Albania (Martinis and Pieri 1964). types of systems (Klimchouk 2007). Despite the fact they can evolve in diferent lithologies (carbonates, evaporites We collected and analyzed samples coming from several and clastic rocks with soluble cement) and geological settings, sulfuric acid environments reported in Figure 1, in particu- they present similar cave patterns and the morphological lar from Porretta Terme thermal spa underground features of rising fow (Klimchouk 2009). Because of the fact (Emilia-Romagna), Monte Cucco and Faggeto Tondo caves they are climate-independent and do not rely on infltrating (Umbria), Montecchio cave (Tuscany), Cavallone and Bove surface waters, the most famous and largest hypogene cave caves (Abruzzo), Cerchiara di Calabria and Cassano allo systems have been found in dry regions (e.g. Carlsbad cav- Ionio Caves (Calabria), Santa Cesarea Terme caves (Apulia), erns and Lechuguilla in the Guadalupe Mountains in New and Acqua Fitusa cave (Sicily). Mexico, Toca da Boa Vista and Toca da Barriguda in Bahia in Brazil, etc). In these areas hypogene cave systems can be preserved afer their exhumation thanks to the dry weather 2. Geological setting conditions, with subduing secondary processes (e.g. epigenic Most SAS caves are located along the Apennine chain, where infltration, deposition of speleothems), which can cover the deep-rooted faults allow groundwaters to rise from depth. In original hypogenic features (Klimchouk et al. 2016). Several many cases these rising fuids are rich in H2S, and more or types of hypogene caves are well known, such as sulfuric acid less thermal. Porretta Terme (Emilia Romagna), Cassano allo (SAS) caves, thermal caves and intrastratal caves in Ionio-Cerchiara di Calabria (Calabria), and Santa Cesarea gypsum (Klimchouk 2009). In Italy all these types of hypo- Terme (Apulia) represent commercially exploited spas and gene caves (Galdenzi and Menichetti 1995; De Waele et al. thermal baths. Montecchio hosts a thermal lake at -100 m, 2014) are documented, but here we focus in particular on sul- Acqua Fitusa is related to a nearby thermal sulfuric spring, furic acid caves that are abundant especially along the Apen- Monte Cucco, Faggeto Tondo, Cavallone and Bove caves are nine Chain, in the Southeast Apulian foreland and in Sicily. high up in the mountains and no longer directly related to Diferently from sulfuric acid caves in the Guadalupe Moun- thermal rising waters. tains (Hose and Macalady 2006), along the Appennine chain Porretta Terme spa is located in the Tuscan-Emilian Apen- the H2S source is mostly related to deep-seated upper Triassic evaporites called “Anidriti di Burano Formation.” (Martinis nines and develops in the “Porretta Terme Formation.”, in particular in the arenitic member called “Arenarie di Suvi-

Proceedings of the 17th International Congress of Speleology 237 Figure 1. Location of the caves object of this study. From the N to the S are reported: Porretta Terme caves in Emilia Romagna, Monte Cucco and Faggeto Tondo caves in Umbria, Montecchio cave in Tuscany, Cavallone and Bove caves in Abruzzo, Cerchiara di Calabria and Cassano allo Ionio caves in Calabria, Santa Cesarea Terme caves in Apulia, Acqua Fitusa cave in Sicily. ana” characterized by Oligocene lithic arenites with a vertical stratifcation due to Apenninic tectonic movements (ISPRA). Figure 2. SAS minerals in several caves in Italy; A) Gypsum depos- Several sulfuric thermal springs have been encountered in an its in Faggeto Tondo cave (credits: J.De Waele); B) Alunite deposits in artifcial network realised in the XIX century. Tese Cavallone cave (credits: M. Nagostinis); C) Gypsum in Sant’Angelo old underground environments are similar to caves, and host Cave in Cassano allo Ionio (credits: O. Lacarbonara); D) Te yellow a wide variety of secondary mineral deposits. deposits are characterized by copiapite, tamarugite and pickeringite and are located in “Sorgente N°3” in Cassano allo Ionio (credits: O. Monte Cucco and Faggeto Tondo caves are located in the Lacarbonara); E and F) Te yellow deposits are characterized by Umbro-Marche Apennines in a fold-and-thrust belt domi- copiapite and tschermigite and are located in Ninfee cave in Cerchiara di Calabria (credits: O. Lacarbonara); G) Sulfur deposits covering nated by carbonate rocks of the “Calcare Massiccio walls and ceiling in Gattulla cave at Santa Cesarea Terme (credits: M. Formation.” (Pialli et al. 1998). Both caves are part of a huge Vattano); H) Gypsum deposits in Acqua Fitusa (credits: M. Vattano). sulfuric acid cave system, uplifed high above the present base level and now abandoned by the sulfuric waters. Te cave is intersected by epigenic vadose shafs and hosts several active Cerchiara di Calabria and Cassano allo Ionio caves are located passages, unrelated to its hypogenic origin. Several fossil con- in the southern Apennines and develop in biogenic calcar- duits still host a variety of secondary minerals related to SAS enites of the “Cerchiara Formation.” of Lower Miocene age speleogenesis. (Selli 1957) and in Triassic dark-grey dolostone (Selli 1962), respectively. Te underground karst network is composed of Montecchio Cave is situated in southern Tuscany, and is various caves and cave levels carved along the former sulfuric hosted in the massive Jurassic limestone of the “Calcare Mas- base level. Te lowest level still contains active sulfuric water siccio Formation.”, and in Lower-Jurassic well-bedded cherty streams, used in the local spas. limestone of the “Calcare selcifero di Limano” (Piccini et al. 2015). It is composed of several cave levels, the lowest of Santa Cesarea Terme caves are located in the south-eastern which (-100 m from the entrance) still hosts a thermal sulfu- Apulian foreland. Tey develop in micritic and ric acid pool. dolostones called “Calcari di Altamura” of Upper age (Azzaroli 1967). Te four caves, all of modest dimensions, Cavallone and Bove caves are located in the central Apen- are carved at sea level and all have a direct access to the sea. nines, in the Majella National Park of Abruzzo, mainly char- Sulfuric thermal waters rise from the fnal parts of the caves acterized by fossiliferous marine limestones deposited during where they meet seawater. upper Cretaceous at the bottom of a tropical sea. Te Majella massif is composed of an anticline fold structure (Patacca et Acqua Fitusa cave is located in the eastern sector of the Sicani al. 1992). Both caves are uplifed trunks of a huge SAS cave Mountains, in San Giovanni in Gemini, Sicily. It forms in the system now partly dismantled by surface erosion, but still breccia member of the Upper Cretaceous known as “Crisanti holding evident signs of its speleogenetic past. Formation.”, characterized by conglomerates and calcarenites with rudists and benthic foraminifera (Catalano et al. 2013).

238 Proceedings of the 17th International Congress of Speleology of Santa Cesarea Terme caves are shown below. Using a high magnifcation (20 μm and 10 μm) it is possible to observe microbial flaments (Fig.3C and D).

All the other sulfates, on the other hand, are all weathering products of sulfuric acid with the host rock, mainly Mg, Al, Fe, K, and Na - containing clay minerals. Among these, the K-jarosite and in particular alunite-group minerals are of extreme interest, because they allow to date the cave-forming process using the radioactive decay of the K-Ar chain (Polyak et al. 1998). Barite, found only in minor amounts in the Monte Cucco cave, might hint to a thermal origin, while fuorite in Faggeto Tondo cave clearly points to very acid and thermal conditions in the initial stages of cave development, before SAS speleogenesis became the dominant process (Forti et al. 1989). Figure 3. SEM images of gypsum and sulfur from Santa Cesarea caves; A) Gypsum crystals, the bar is 100 μm; B) Gypsum and sulfur crystals, the bar is 100 μm; C) In the white square it is possible to 4. Concluding remarks observe a flamentous structure between a gypsum crystal and sulfur In this study we report the results of mineralogical studies on minerals, the bar is 20 μm; D) In the white square it is possible to observe a flament in sulfur deposits, the bar is 10 μm. secondary cave minerals formed by the interaction of sulfuric acid with the host rock. A total of 15 SAS caves have been Acqua Fitusa is a marvellous example of a sulfuric water table visited and minerals have been collected. Also the artifcial cave (De Waele et al. 2016), now disconnected from the active tunnels of a sulfuric thermal spa have been investigated. spring below. Eleven minerals have been identifed, most of which are sulfates (9), while native sulfur has been found in three loca- 3. Results tions and fuorite in only one cave. Besides the well-known Te collected samples have been analyzed using XRD meth- SAS minerals (gypsum, jarosite, alunite), also less common odology in Genova and Modena-Reggio Emilia Universities. minerals such as copiapite, tamarugite, tschermigite and Some preliminary analyses with Scanning Electron Micro- pickeringite have been discovered. Copiapite-group miner- scope have been done in the laboratory of Bologna University. als, besides volcanic caves close to fumarolic activity (Hill and Forti 1996), have been observed in mine environments and In the following table (Table 1) the eleven SAS minerals found in particular in inactive mines of massive sulfde deposits in in these sulfuric acid environments are listed. Tese miner- California (Jamienson et al., 2005) and in Sardinia (Bini et al. als generally occur as crusts or microcrystalline powdery 1986; De Waele and Forti 2005; Ara et al. 2013). It has also deposits of pale white to yellowish and orange color. Larger been reported from one sulfuric acid cave, Carlsbad Caverns crystals have also been found occasionally (mainly gypsum (Mosch and Polyak 1996). Tamarugite and pickeringite have and sulfur) (Fig. 2). previously been described in relation with fumarolic activity in volcanic caves (Hill and Forti 1996), and in two sulfuric Gypsum is derived from the typical reaction of sulfuric acid acid environments as well, Diana Cave in Romania (Puşcaş with pure limestone (calcite), producing also CO2 (Galdenzi et al. 2013) and Aghia Paraskevi in Greece (Lazaridis et al. and Maruoka 2003). Sulfur is instead formed in extremely 2011). Tschermigite deposits have been discovered in thermal acidic conditions with the intermediation of micro-organ- sulfdic serpents cave in France by Audra and Hobléa (2007) isms. SEM images (Fig.3) from gypsum and sulfur deposits in association with alunogen and jurbanite, and in Lone

Table 1. Te eleven secondary SAS minerals in the studied caves: PT = Porretta Terme, MC = Monte Cucco, FT = Faggeto Tondo, MT = Mon- tecchio, CB = Cavallone-Bove; CC = Cerchiara di Calabria-Cassano allo Ionio, SCT = Santa Cesarea Terme, AF = Acqua Fitusa.

SAS Minerals Chemical formula PT MC FT MT CB CC SCT AF

Gypsum CaSO4 2H2O x x x x x x x x

K-Jarosite KFe(SO4)2(OH)6 x x x x x x x Sulfur S0 x x x

Alunite KAl3(SO4)2(OH)6 x x x

Barite BaSO4 x

Fluorite CaF2 x

Natroalunite NaAl3(SO4)2(OH)6 x 2+ 3+ Copiapite Fe Fe 4 (SO4)6(OH)2 *20H2O x

Pickeringite MgAl2(SO4)4*22H2O x

Tamarugite NaAl(SO4)2 *6H2O x

Tschermigite (NH4)Al(SO4)2 *12H2O x

Proceedings of the 17th International Congress of Speleology 239 Creek Fall Cave in eastern Transvaal, where it derives from 2014. A review on hypogenic caves in Italy. In: AB Klim- pyrite oxidation and decay of guano, in the presence of clays chouk, I Sasowsky, J Mylroie, S Engel, A Engel Summers (Martini 1983). (Eds.), Hypogene Cave Morphologies. Selected papers and abstracts of the symposium held February 2 through 7, 2014, Some of these minerals can allow in the future to date the San Salvador Island, Bahamas. Karst Waters Institute Special cave-forming process, with the possibility to constrain the Publication 18, Karst Waters Institute, Leesburg, Virginia, formation of the very old caves of Cavallone and Bove, and pp. 28-30. maybe also Monte Cucco. De Waele J, Audra P, Madonia G, Vattano M, Plan L, Acknowledgements D’Angeli IM, Bigot JY, Nobécourt JC, 2016. Sulfuric acid speleogenesis (SAS) close to the water table: Examples from Many thanks to Orlando Lacarbonara and Maria Nagostinis southern France, Austria, and Sicily. Geomorphology, 253, for help during sampling and their pictures of samples. Field- 452-467. work in Calabria was made comfortable and pleasant thanks to Carlo Forace, Peppino Martire and Salvatore Casalnuovo Forti P, Menichetti, M, Rossi A, Hazslinszky T, Takacsne of the Associazione Speleologica Liocorno of Cassano allo BK, 1989. Speleothems and speleogenesis of the Faggeto Ionio, the staf of Terme Sibarite spa, Antonio Cesarini, Serra Tondo cave (Umbria, Italy). In: Proceedings 10th International del Gufo speleological group and Grotta delle Ninfee thermal Congress of Speleology, Budapest, Vol. 1., pp. 74-76. spa. Activity in Apulia was possible thanks to availability of the staf at Santa Cesarea Terme. Sampling in Monte Cucco Galdenzi S, Maruoka T, 2003. Gypsum deposits in the Cave was done in company of Giuseppe (Pino) Antonini. Frasassi Caves, central Italy. Journal of Cave and Karst Stud- ies, 65(2), 111-125. SEM images were performed at the University of Bologna with the assistance of Prof. Giorgio Gasparotto. Galdenzi S, Menichetti M, 1995. Occurrence of hypogenic caves in a karst region: examples from central Italy. Environ- mental Geology, 26, 39-47. References Ara D, Sanna L, Rossi A, Galli E, De Waele J, 2013. Minerali Hose LD, Macalady JL, 2006. Observation from active secondari in ambiente sotterraneo: la miniera dell’Argentiera sulfdic karst systems: is presented the key to understanding (Sardegna nord-occidentale). In: F Cucchi and P Guidi P. Guadalupe Mountain speleogenesis? In: L Land, P Boston, D (Eds.), Atti del XXI Congresso Nazionale di Speleologia “Dif- Love (Eds), Cave and karst of Southeastern New Mexico: New fusione delle conoscenze”, Trieste, pp. 290-295. Mexico Geol. Soc. Guidebook, 57, 185-194.

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